Recyclable Chiral Imidazolidinone Catalyst for α-Alkylation of Aldehydes

Stereoselective aldol reaction catalyzed by a highly recyclable polystyrene supported substituted prolinamide catalyst

Polystyrene supported substituted prolinamide was used as catalyst in the aldol reaction between cyclohexanone or acetone and several substituted benzaldehydes in chloroform/water. This catalyst afforded aldol products in high yields and stereoselectivities, especially in the case of reactions performed with acetone. The catalyst was easily recovered by filtration and reused, after regeneration with formic acid, up to 22 times.

Cross-Linked Polyamine from Imidazolium-Based Materials: A Simple Route to Useful Catalytic Materials

Cross-linked polyamine-based materials were easily prepared by reduction of the corresponding cross-linked imidazolium-based materials with sodium borohydride in hot ethanol. Overall, the synthetic procedure is based on the polymerization of a suitable bis-vinylimidazolium salt with or without a suitable support, such as silica or silica-coated magnetic nanoparticles (γ-Fe2O3@SiO2), followed by reduction. This simple approach allows the synthesis of materials based on a network of secondary and tertiary amines. Materials were characterized by13C cross-polarization magic angle spinning NMR (13C CPMAS NMR), proton spin-lattice relaxation times in the rotating frame (T1ρH) and thermogravimet…

Recyclable Heterogeneous and Low-Loading Homogeneous Chiral Imidazolidinone Catalysts for α-Alkylation of Aldehydes

Two polystyrene-supported and six homogeneous MacMillan imidazolidinone catalysts were prepared and tested for the asymmetric α-alkylation of propanal with benzodithiolylium tetrafluoroborate. The chiral imidazolidinone was linked to polystyrene through the N-3 atom or through the phenyl ring and their catalytic activity was compared with that of their unsupported precursors. This comparison has allowed us to find an unsupported catalyst that displays high catalytic activity down to 5 or 2 mol % at room temperature with a high level of enantioselectivity also when used with hexanal and 3-phenylpropanal. In addition, one of the heterogeneous materials was revealed to be highly recyclable for…

New substituted imidazolidinone as low loading catalyst for α-alkylation of aldehydes

Proline- and prolinamide-supported polystyrene: powerful and highly recyclable organocatalysts for the asymmetric aldol reaction

Simple and low loading catalysts for asymmetric aldol reaction under aqueous condition

Advances in organic and organic-inorganic hybrid polymeric supports for catalytic applications

In this review, the most recent advances (2014–2016) on the synthesis of new polymer-supported catalysts are reported, focusing the attention on the synthetic strategies developed for their preparation. The polymer-supported catalysts examined will be organic-based polymers and organic-inorganic hybrids and will include, among others, polystyrenes, poly-ionic liquids, chiral ionic polymers, dendrimers, carbon nanotubes, as well as silica and halloysite-based catalysts. Selected examples will show the synthesis and application in the field of organocatalysis and metal-based catalysis both for non-asymmetric and asymmetric transformations.

Immobilizzazione di dipeptidi su resina polistirenica ed impiego in sintesi stereoselettive: risultati preliminari

Multi-layered, covalently supported ionic liquid phase (mlc-SILP) as highly cross-linked support for recyclable palladium catalysts for the suzuki reaction in aqueous medium

The reaction between an excess of 1,4-bis(3-vinylimidazolium-1-yl) bromide and a mercaptopropyl-modified amorphous silica gel or ordered mesoporous silica SBA-15 in the presence of azobisisobutyronitrile (AIBN) afforded new materials, which have a high loading of imidazolium moieties. These materials, which contain a highly cross-linked polymeric network, have been denoted as multi-layered, covalently supported ionic liquid phase (mlc-SILP) and have been used as support for palladium catalysts containing a high loading of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–Emmett–Teller technique, sma…

DNA-Binding and Anticancer Activity of Pyrene-Imidazolium Derivatives

DNA-binding investigations showed that two different derivatives endowed with pyrene and imidazolium moieties, 1 and 2, strongly bind both double-stranded DNA and telomeric sequences in G-quadruplex (G4) conformation. The values of the DNA-binding constants indicate that 1 and 2 show preferential affinity for G4-DNA, of about one and two orders of magnitude, respectively. Moreover, 1 and 2 inhibit short and long-term proliferation of breast cancer cell lines in a time- and dose-dependent fashion. Remarkably, senescence assays indicate that telomeric G4-DNA is a possible biotarget for the cytotoxic activity of 2. Molecular dynamics simulations suggest that the stronger binding of 2 with G4-D…

Sali di imidazolio multistrato supportati covalentemente: attività catalitica per la produzione di carbonati ciclici in scCO2 e nuovi supporti per catalizzatori di palladio

I liquidi ionici supportati (SILP) hanno trovato interessanti applicazioni sia nel campo delle reazioni catalizzate da metalli che in organocatalisi [1]. Inoltre, i SILP sono stati efficacemente impiegati in reazioni di apertura di epossidi in CO2 supercritica per fornire carbonati ciclici [2]. I liquidi ionici vengono generalmente supportati covalentemente attraverso la modificazione dei gruppi funzionali presenti sulla superficie del supporto, conducendo in tal modo alla formazione di un monostrato di liquido ionico supportato. Gli esempi di SILP legati covalentemente, in maniera tale da ottenere dei multistrato, sono rari. In questa comunicazione viene riportato un metodo per preparare d…

A Simple Procedure for Oxidation of Alcohols using [Bis(acetoxy)iodo]benzene and a Catalytic Amount of Bromide Ions in Ethyl Acetate

Primary and secondary benzylic alcohols and secondary aliphatic alcohols were oxidized to the corresponding aldehydes and ketones by using [bis(acetoxy)iodo]benzene (BAIB) and a catalytic amount of bromide ions, from tetrabutylammonium bromide or KBr, in ethyl acetate. The catalytic role of the bromide ions was also highlighted in the oxidation of primary aliphatic alcohols and secondary allylic alcohols carried out in the presence of 1 mol% TEMPO.

Cross-Linked Polyamine from Imidazolium-Based Materials: A Simple Route to Useful Catalytic Materials

Enhanced Activity and Stereoselectivity of Polystyrene-Supported Proline-Based Organic Catalysts for Direct Asymmetric Aldol Reaction in Water

Several polystyrene-supported proline dipeptides and a prolinamide derivative were prepared by thiol–ene coupling. These materials were used as catalysts for the direct asymmetric aldol reaction in water, and results compared with unsupported catalysts in water. Such an approach gave more active or stereoselective catalysts compared to the unsupported compounds, showing that our immobilization procedure may be useful to develop catalytic materials with enhanced performance. Moreover, these catalysts can be recovered and reused for at least nine times without loss of activity or can be easily regenerated when their activity has decreased. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, …

ChemInform Abstract: A Simple Procedure for the Oxidation of Alcohols Using [Bis(acetoxy)iodo]benzene and a Catalytic Amount of Bromide Ions in Ethyl Acetate.

Primary and secondary benzylic alcohols and secondary aliphatic alcohols were oxidized to the corresponding aldehydes and ketones by using [bis(acetoxy)iodo]benzene (BAIB) and a catalytic amount of bromide ions, from tetrabutylammonium bromide or KBr, in ethyl acetate. The catalytic role of the bromide ions was also highlighted in the oxidation of primary aliphatic alcohols and secondary allylic alcohols carried out in the presence of 1 mol% TEMPO.

Evidences of release and catch mechanism in the Heck reaction catalyzed by palladium immobilized on highly cross-linked-supported imidazolium salts

Abstract Palladium (10 wt%) on a highly cross-linked imidazolium-based material was used as catalyst in 0.1 mol% in the Heck reaction between several alkenes and aryl iodides. Products were obtained from good to high yields. Deeper investigations showed a release of Pd species in solution and their capture by the imidazolium-based support. When a sixfold amount of support was employed the re-captured Pd species (0.5–0.6 wt%) were not anymore catalytically active. This result represents a new interesting aspect of this work since the highly cross-linked imidazolium-based material can act also as Pd scavenger avoiding the release of the metal in solution. Important differences between Heck an…

Novel supported dipeptides as recyclable catalysts for asymmetric aldol reaction

Highly Loaded Multi-Walled Carbon Nanotubes Non-Covalently Modified with a Bis-Imidazolium Salt and their Use as Catalyst Supports

The surfaces of multi-walled carbon nanotubes (MWCNTs) were non-covalently modified using two bis-imidazolium dibromide derivatives having phenyl or pyrene groups. Due to the presence of the two pyrene groups the bis(pyren-1-ylmethylimidazolium) dibromide derivative was immobilised at a loading of about 15-16 wt %, whereas only <3 wt % of the phenyl derivative was immobilised. The presence of the two imidazolium cations helped the immobilisation of tetrachloropalladate ions after exchange with bromide ions. Tetrachloropalladate was used as pre-catalyst in several Suzuki-Miyaura carbon-carbon cross-coupling reactions in water or water/ethanol at 50 °C in only 0.1 mol % and compared with the …

New proline derivatives as recyclable catalysts for aldol reaction

ChemInform Abstract: Enhanced Activity and Stereoselectivity of Polystyrene-Supported Proline-Based Organic Catalysts for Direct Asymmetric Aldol Reaction in Water.

Several polystyrene-supported proline dipeptides and a prolinamide derivative were prepared by thiol–ene coupling. These materials were used as catalysts for the direct asymmetric aldol reaction in water, and results compared with unsupported catalysts in water. Such an approach gave more active or stereoselective catalysts compared to the unsupported compounds, showing that our immobilization procedure may be useful to develop catalytic materials with enhanced performance. Moreover, these catalysts can be recovered and reused for at least nine times without loss of activity or can be easily regenerated when their activity has decreased. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, …

Novel supported substituted prolinamide as recyclable catalyst for asymmetric aldol reaction